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The Upanishads (उपनिषद्) are part of the Hindu Shruti scriptures which primarily discuss meditation and philosophy and are seen as religious instructions by most schools of Hinduism.
They also contain transcripts of various spiritual debates or discussions, and of the 123 books considered to be part of the Upanishads, 12 are accepted by all Hindus as primary.
The term Upanishad derives from the Sanskrit words upa (near), ni (down) and s(h)ad (to sit) i.e., sitting down near; implying the act of listening to a spiritual teacher. The Upanishads are commentaries on the Vedas, their putative end and essence, and thus known as Vedanta ("End of the Veda").
Different Upanishads serve as commentaries or extensions of each of the four Vedas (Rig, Yajur, Sama and Atharva). The oldest and longest of the Upanishads are the Brihad-Aranyaka and the Chandogya ; scholars vary on when they first were written and estimates range the 16th to 7th century BCE. There is great scholarly consensus that many of the early Upanishads are pre-Buddhistic. Initially there were over two hundred Upanishads but only fifteen or so were considered to be primary by the philosopher Shankara. The Upanishads were not fully recorded until 1656, at the order of Dara Shakoh .
These philosophical and meditative tracts form the backbone of Hindu thought. Of the early Upanishads, the Aiterya and Kaushitaki belong to the Rig Veda, Kena and Chandogya to the Sama, Isha and Taittereya and Brihadaranyaka to the Yajur, and Prasna and Mundaka to the Atharva. (associated Upanishad and Vedic book taken from Radhakrishnan Indian Philosophy, Vol. 1)
In addition, the Mandukya, Katha, Svetashvatara are very important. Others also include Mahanarayana and Maitri Upanishads as key.
A site that does well in summarizing the Upanishads is to be found here: http://www.indianest.com/hinduism/037.htm
Often, critics of the Hindu/Vedic tradition will use the term Brahminical to imply a karma-kanda, or ritual-based mode of worship, a sacerdotalism that loses sight of deeper spirituality. However, it is widely acknowledged that those who wrote the mystic verse of the Upanishads were in all likelihood Brahmins as well.
Scholarly breakdowns of the Vedic books see the four Vedas as poetic liturgy, collectively called mantras or samhitas, adoration and supplication to a sort of melded monist and henotheist notion of the Gods/Goddesses and an overarching Order ( Rta) that transcended even the Gods and stemmed from One Ultimate Source.
The Brahmanas were a collection of ritual instructions, books detailing the priestly functions (which first were available to all men, and so concretized into strictly Brahmin privilege). These came after the Mantras.
Then we have the Upanishads, which consist of the Aranyakas and Upanishads. Aranyaka means forest, and these most probably grew as a sort of subtle rejection of the Brahmanas: they detail meditative yogic practices, contemplations of the mystic one and the manifold manifested principles. The Upanishads, finally, meaning 'Sitting Near' (implied are the Guru's sacred feet), culminate. The Upanishads basically realized all the monist and universal mystical ideas that saw their nascence in earlier Vedic hymns, and have exerted an influence unprecedented on the rest of Hindu and Indian philosophy. However, by adherents they are not considered philosophy alone, and form meditations and practical teachings for those advanced enough to benefit from their wisdom.
The Taittiriya Upanishad says this in the Ninth Chapter:
"He who knows the Bliss of Brahman, whence words together with the mind turn away, unable to reach It?he is not afraid of anything whatsoever. He does not distress himself with the thought Why did I not do what is good? Why did I do what is evil? Whosoever knows this regards both these as Atman; indeed he cherishes both these as Atman. Such, indeed, is the Upanishad, the secret knowledge of Brahman."